Introducing restricted rotation in a molecule, often achieved through the incorporation of double or triple bonds, constitutes a crucial approach to induce a frustrated mesophase. Furthermore, the inclusion of a chiral moiety, such as cholesterol, serves to enhance the stabilization of chiral frustrated mesophases. This study presents the synthesis and characterization of novel optically active dimers incorporating cholesterol and phenyl 3-phenylpropiolate segments interconnected by an ω-oxyalkanoyloxy spacer with varying lengths and parity. Comprehensive characterization using POM, DSC, and X-ray diffraction techniques reveals that these mesogens exhibit enantiotropic liquid crystal (LC) phases. Due to the restricted rotation caused by the triple bonded system, these dimers stabilized the frustrated chiral mesophase TGBC* over a wide temperature range. The identified phases include BP-I/II, N*, and SmA, with odd-membered dimers commonly displaying N* and SmA phases and one member additionally exhibiting BP-I/II. Even-membered dimers exhibit N* and TGBC* phases, with the latter spanning an impressive thermal range of 37 °C to 84 °C. Notably, the thermal range of the TGBC* phase widens with an increase in the terminal tail length. Across the series, clearing temperatures generally decrease with the elongation of the terminal tail, and even-membered dimers consistently exhibit higher clearing temperatures than their odd-membered counterparts, illustrating the spacer's parity-dependent odd-even effect on the dimers' phase transition behavior.